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US10656130B2 - Elemental analysis system and method with a reactor having two metal zeolite nitrogen oxides reduction reaction zones - Google Patents

Elemental analysis system and method with a reactor having two metal zeolite nitrogen oxides reduction reaction zones Download PDF

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US10656130B2
US10656130B2 US15/582,965 US201715582965A US10656130B2 US 10656130 B2 US10656130 B2 US 10656130B2 US 201715582965 A US201715582965 A US 201715582965A US 10656130 B2 US10656130 B2 US 10656130B2
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reactor
reaction zone
reduction reaction
mass
nitrogen
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Antonella Guzzonato
Christopher Brodie
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Thermo Fisher Scientific Bremen GmbH
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0011Sample conditioning
    • G01N33/0013Sample conditioning by a chemical reaction
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/12Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/0027Methods for using particle spectrometers
    • H01J49/0031Step by step routines describing the use of the apparatus
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/025Detectors specially adapted to particle spectrometers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N2030/067Preparation by reaction, e.g. derivatising the sample
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8868Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample elemental analysis, e.g. isotope dilution analysis

Definitions

  • Elemental analysis (EA) involving combustion/reduction and/or pyrolysis is a widely used technique for the quantification of elemental concentrations of hydrogen, carbon, nitrogen, oxygen, and sulphur in organic and inorganic materials.
  • Interfaced with isotope ratio mass spectrometry (IRMS) EA is commonly employed as a technique for the measurement of stable isotope ratios of the aforementioned elements. See Calderone et al, (2004) J. Agric. Food Chem., 52, 5902-5906, and Fadeeva et al, (2008) J. Anal. Chem.
  • the ⁇ -notation is the stable isotope ratio of an unknown sample relative to a standard (i.e. reference material) of known isotope value, calculated as:
  • the analysis of hydrogen, carbon, nitrogen and sulphur is achieved by combusting a sample matrix in a reactor held at a temperature in a range of between 400° C. and 1,100° C., but ideally in a range of between 950° C. and 1,100° C.
  • samples are sealed in tin capsules (alternatively, silver or aluminum capsules) and introduced to the combustion reactor by an autosampler in a flow of carrier gas, such as helium (for EA-IRMS), or argon or nitrogen (EA analysis only).
  • carrier gas maintains pressure and temperature regimes in the reactor, minimizes introduction of contaminant gases, such as air, and reduces damage to any materials or chemicals inside the system.
  • Elemental analyzers require carrier flows of up to 1,000 ml/min depending on the volume to be flushed, the largest volume generally being the reactor.
  • the typical operating flow rate through the reactor is in the range of between 0.2 ml/min and 300 ml/min, such as in the range of between 40 ml/min and 300 ml/min, or between 40 ml/min and 200 ml/min (EA analysis only), depending on the reactor size, and a purge flow to the autosampler is generally in a range of between 20 ml/min and 300 ml/min.
  • an injection of oxygen gas may or may not occur, depending on the sample matrix, to support the combustion process (Lott et al, Rapid Commun. Mass Spectrom. 2015, 29, 1-8), hereby incorporated by reference in its entirety (however, where anything in the incorporated reference contradicts anything stated in the present application, the present application prevails).
  • the sample matrix breaks down, and is conveyed by the carrier gas across an oxygen donor compound (e.g., Cr 2 O 3 , WO 3 ), which is designed to ensure complete oxidation of the carbon, nitrogen and sulphur elements evolved from the sample matrix to gaseous oxidized products (e.g., CO 2 , NO x , SO 2 ).
  • an oxygen donor compound e.g., Cr 2 O 3 , WO 3
  • the next step in the reaction varies depending on the set-up of the system.
  • Approach 1 two reactor system
  • the gases are then optionally swept across a sulphur/halogen trap and transferred to a reduction reactor, typically via a stainless steel/sulfinert capillary or heated bridge, which contains metallic copper.
  • the gases are carried out of the reduction reactor, they are swept through a water trap (e.g., magnesium perchlorate) and/or optionally a CO 2 /acid gas trap (e.g., carbosorb) before being analyzed.
  • a water trap e.g., magnesium perchlorate
  • a CO 2 /acid gas trap e.g., carbosorb
  • the gases are typically separated on a gas chromatography column or by an adsorption/thermodesorption technique prior to analysis by a thermal conductivity detector (TCD), a flame ionization detector (FID), or an isotope ratio mass spectrometer.
  • TCD thermal conductivity detector
  • FID flame ionization detector
  • a sulphur/halogen trap may also be present in the lower section of the reactor (e.g., AgCoO 4 or silver wool). Thereafter, the gas is conveyed from the reactor through a water trap and/or optionally a CO 2 /acid gas trap before gas separation and detection as in Approach 1.
  • a stoichiometric combustion and reduction reaction pathway is necessary for the accurate and precise determination of percent elemental and isotopic measurements of carbon, nitrogen and sulphur.
  • the process is designed to produce N 2 gas for detection by the TCD and/or isotope ratio mass spectrometer.
  • nitrogen compounds are broken down and subsequently form nitrogen oxides (NO x ). These oxides of nitrogen must be stoichiometrically reduced to N 2 , which is one of the functions of the metallic Cu in the reactor(s) described in Approach 1 and Approach 2.
  • an elemental analysis system includes a reactor having at least one reduction reaction zone including a metal zeolite that can reduce nitrogen oxides (NO x ) to molecular nitrogen (N 2 ) by selective catalytic reaction.
  • a method of elemental analysis includes providing a reactor having at least one reduction reaction zone including a metal zeolite and reducing nitrogen oxides (NO x ) to molecular nitrogen (N 2 ) by selective catalytic reaction on the metal zeolite.
  • the metal zeolite can be a ZSM-5 type material.
  • the metal zeolite typically ZSM-5 type, can have one or more of the following beneficial characteristics: a MFI framework type, a BET surface area of at least 300 m 2 /g, and/or a weight loss on ignition of less than 12 wt %.
  • the metal zeolite can include a +2 oxidation state metal, such as at least one of copper, platinum, nickel, and cobalt.
  • the metal content of the metal zeolite can be in a range of between 2.1 wt % and 5.0 wt %.
  • the metal zeolite can have a grain size in a range of between 0.3 mm and 2.9 mm, such as in a range of between 1 mm and 2 mm, or, in a specific embodiment, the grain size of the metal zeolite can be 1.6 mm.
  • the metal zeolite can include carbon in an amount that is at least 70 ppm and less than 200 ppm.
  • the at least one reduction reaction zone can be one zone packed in a single packing unit having a length that is in a range of between 1% and 30% of a length of the reactor.
  • the at least one reduction reaction zone can be at least two reduction reaction zones of substantially the same length, the lengths being in total in a range of between 1% and 30% of a length of the reactor, i.e., of the total length of the reactor.
  • the at least one reduction reaction zone can be at least two reduction reaction zones of different lengths, such as successively increasing lengths in a direction of gas flow through the reactor, the lengths being in total in a range of between 1% and 30% of a length of the reactor.
  • the zones can be separated from each other by a porous material, the separation having a length in a range of between 1% and 3% of a length of the reactor.
  • the porous material can include quartz or glass wool.
  • the at least two reduction reaction zones can be two reduction reaction zones, each reduction reaction zone having a length in a range of between 1% and 15% of a length of the reactor.
  • the at least two reduction reaction zones can be three reduction reaction zones, such as three reduction reaction zones of successively increasing lengths in a direction of gas flow through the reactor.
  • the reactor can further include an oxidation reaction zone, the oxidation reaction zone being located before, i.e., upstream of, the reduction reaction zone in a direction of gas flow through the reactor.
  • the method of elemental analysis can include providing an oxidation reaction zone located before, i.e., upstream of, the reduction reaction zone in a direction of gas flow through the reactor, for oxidizing a sample.
  • the sample oxidation in the oxidation reaction zone can include generating combustion product gases including NO x .
  • the combustion product gases can include at least one of CO 2 and SO 2 /SO 3 .
  • the reactor can further include an oxygen gas inlet upstream of or into the oxidation reaction zone.
  • the oxidation reaction zone can include an oxygen-donor material, such as at least one of chromium trioxide (Cr 2 O 3 ), tungsten trioxide (WO 3 ), copper oxide, and a mixture of copper oxide and platinum-coated aluminum oxide.
  • an oxygen-donor material such as at least one of chromium trioxide (Cr 2 O 3 ), tungsten trioxide (WO 3 ), copper oxide, and a mixture of copper oxide and platinum-coated aluminum oxide.
  • the elemental analysis system further includes a furnace to heat the reactor, wherein the reduction reaction zone and oxidation reaction zone are each configured to be heated to a temperature in the range of between 150° C. and 1,200° C., such as a temperature in the range of between 750° C. and 1,200° C., or a temperature in the range of between 950° C. and 1,100° C.
  • the reduction reaction zone can be configured to be heated to a different temperature from the oxidation reaction zone, such as a lower temperature than the oxidation reaction zone.
  • the elemental analysis system can include an oxygen capture zone, downstream of the reduction reaction zone in a direction of gas flow through the reactor, which can include metallic copper, metallic platinum, metallic nickel, or metallic cobalt, or any combination thereof.
  • the oxygen capture zone can act to remove gaseous oxygen from the gases passing out of the reduction reaction zone.
  • the elemental analysis system can further include a second reactor in fluid communication with the first reactor that contains the reduction reaction zone, the second reactor being located upstream of the first reactor in a direction of gas flow through the first reactor, the second reactor including an oxidation reaction zone.
  • the elemental analysis system can further include a furnace to heat the first reactor to a temperature in the range of between 150° C. and 1200° C., such as a temperature in the range of between 150° C. and 1100° C., or a temperature in the range of between 450° C. and 900° C., and a second furnace to heat the second reactor to a temperature in the range of between 150° C. and 1,200° C.
  • the temperature of the second reactor can be in the range of between 750° C. and 1,200° C., such as in the range of between 950° C. and 1,100° C.
  • the first and second reactors can be located in, i.e., heated by, a single, common furnace.
  • the second reactor can further include an oxygen gas inlet upstream of or into the oxidation reaction zone.
  • the oxidation reaction zone can include an oxygen-donor material, such as at least one of chromium trioxide (Cr 2 O 3 ), tungsten trioxide (WO 3 ), copper oxide, and a mixture of copper oxide and platinum-coated aluminum oxide.
  • the reactor containing the reduction reaction zone can be interfaced to a gas chromatography column located downstream of the reactor in a direction of gas flow.
  • the reactor can be interfaced with a mass spectrometer located downstream of the reactor in a direction of gas flow through the reactor, optionally an isotope ratio mass spectrometer.
  • the gas chromatography column can be interfaced to a thermal conductivity detector (TCD), a flame ionization detector (FID), an infrared (IR) detector, or a mass spectrometer, such as an isotope ratio mass spectrometer.
  • the mass spectrometer can be located downstream of the gas chromatography column in a direction of gas flow, optionally an isotope ratio mass spectrometer including a magnetic sector mass analyzer.
  • the isotope ratio mass spectrometer can have a multicollector detection system for simultaneously detecting two or more spatially separated ion beams, which consist of ions differing in their mass due to the isotopic differences in the gas molecules of the ions. Measurements of these ion beams in multicollector systems allow isotope ratios to be determined.
  • the first reactor can be interfaced to a gas chromatography column or a mass spectrometer, as described in the preceding paragraph.
  • the elemental analysis system can include a sample introduction system, such as an autosampler located upstream from the reactor for introducing liquid or solid samples into the system.
  • the elemental analysis system can include a sample introduction system, such as an autosampler located upstream from the second reactor for introducing liquid or solid samples into the system.
  • a method of elemental analysis of a sample includes introducing into an oxidation reaction zone a sample to be analyzed, optionally using a liquid or solid autosampler, oxidizing the sample in the oxidation reaction zone to generate oxidized products including nitrogen oxides (NO x ) from nitrogen present in the sample, reducing the nitrogen oxides to elemental nitrogen in a reactor including at least one reduction reaction zone including a metal zeolite that can reduce nitrogen oxides (NO x ) to molecular nitrogen (N 2 ) by selective catalytic reaction, and analyzing the elemental nitrogen using mass spectrometry.
  • NO x nitrogen oxides
  • N 2 molecular nitrogen
  • the analyzing can include analyzing the molecular nitrogen (N 2 ) using isotope ratio mass spectrometry (IRMS) and determining therefrom a ⁇ 15 N value for the nitrogen produced from the sample material.
  • the analyzing can include analyzing the molecular nitrogen (N 2 ) using isotope ratio mass spectrometry (IRMS) and determining therefrom isotope abundances or an isotope ratio such as [14]N/[14]N (mass 28 ), [15]N/[14]N (mass 29 ), and/or [15]N/[15]N (mass 30 ), as raw isotope ratios and subsequently converting them to ⁇ 15 N values for the nitrogen produced from the sample material, or determining % N of the sample.
  • IRMS isotope ratio mass spectrometry
  • the mass 30 peak can elute substantially simultaneously with the mass 28 and mass 29 peaks in the IRMS analysis. This is indicative that the mass 30 peak is due to [15]N 2 and not [14]N[16]O and therefore that substantially complete NO x to N 2 reduction has taken place.
  • the method can further include introducing oxygen upstream of and into the oxidation reaction zone.
  • the invention has many advantages, including enabling improved accuracy and precision of measured ⁇ 15 N values, obtaining a mass 30 ion trace that is proportional to the mass 28 and mass 29 ion traces, in line with expected nitrogen isotope proportions at natural abundance levels, which elutes simultaneously and remains stable throughout the lifetime of the reactor, and is linearly related to the mass 28 and mass 29 ion traces. Additionally, it has significant potential for applications analyzing samples enriched in [15]N relative to natural abundance levels, such as tracer studies.
  • the invention can enable more efficient production of N 2 gas from a sample for detection by a TCD, and/or isotope ratio mass spectrometer, giving more accurate nitrogen analysis as a result of the oxides of nitrogen (NO x ) being more stoichiometrically reduced to N 2 before the analyte gas is conveyed from the reactor for separation and subsequent analysis by the TCD and/or IRMS.
  • the reactor of the present invention can be used in EA systems to analyze other elements, such as % C and/or ⁇ 13 C, and % S and/or ⁇ 34 S.
  • Mass spectrometry such as IRMS, can be used to analyze the combustion products such as CO 2 or SO 2 formed in the system.
  • a method of elemental analysis of a sample includes introducing into an oxidation reaction zone a sample to be analyzed, oxidizing the sample in the oxidation reaction zone to generate oxidized products from elements present in the sample, reducing one or more oxidized products in a reactor including at least one reduction reaction zone including a metal zeolite, and analyzing an elemental and/or isotopic composition from one or more of the oxidized products using gas chromatography and/or mass spectrometry.
  • the elements can be carbon, sulphur, and/or nitrogen.
  • the analyzing can include analyzing the oxidized products using isotope ratio mass spectrometry (IRMS) and determining therefrom an isotope ratio. Further details of the IRMS are given elsewhere herein.
  • FIG. 1 is a chromatogram illustrating the mass 28 , 29 , and 30 ion trace behavior in elemental analysis using a reactor of a type known in the art for 40 years.
  • FIG. 2A is a schematic illustration of a single reactor elemental analysis system according to an exemplary embodiment of the invention.
  • FIG. 2B is a schematic illustration of a reactor including three reduction reaction zones according to an exemplary embodiment of the invention.
  • FIG. 2C is a schematic illustration of a reactor including one reduction reaction zone according to an exemplary embodiment of the invention.
  • FIG. 2D is a schematic illustration of a reactor including two reduction reaction zones according to an exemplary embodiment of the invention.
  • FIG. 3A is a schematic illustration of a two reactor elemental analysis system according to an exemplary embodiment of the invention.
  • FIG. 4 is a flowchart of a method of elemental analysis of a sample according to an exemplary embodiment of the invention.
  • FIG. 6 is a graph of the mass 30 ion trace as a function of the mass 28 ion trace showing a linear correlation between intensity of the mass 30 and mass 28 ion traces from 166 contiguous samples processed within one reactor according to an exemplary embodiment of the invention.
  • FIG. 7 is a schematic illustration of an elemental analysis system according to an exemplary embodiment of the invention having a GC column interfaced to the inlet of a reactor.
  • FIG. 8 is a schematic illustration of an elemental analysis system according to another exemplary embodiment of the invention having a GC column interfaced to the inlet of a reactor.
  • FIG. 9 is a set of chromatograms obtained from sample analysis from a GC-MS elemental analysis system according to a single reactor prior art embodiment.
  • mass 30 is not typically used in calculations is that, using the reactors available on the market today, the mass 30 ion trace 110 will gradually rise over the course of the first 1-10 samples, as illustrated in FIG. 1 , and remain high throughout the remainder of the analysis. It is also common for the mass 30 ion trace 110 to come close to or exceed the dynamic range of the isotope ratio mass spectrometer, as shown in FIG. 1 , meaning that the signal is greater than the dynamic range of the isotope ratio mass spectrometer. It can be clearly seen in FIG.
  • the intensity of the mass 30 ion trace 110 is much higher than the mass 28 ion trace 120 and the mass 29 ion trace 130 , the mass 28 ( 120 ) and mass 29 ( 130 ) traces resulting only from N 2 species.
  • the intensity of the mass 30 ion trace 110 is not linearly related to the mass 28 ( 120 ) and mass 29 ( 130 ) ion traces, respectively, as expected at natural abundance levels for nitrogen isotopes, and the chromatographic peak center of the mass 30 ion trace 110 is delayed with respect to the mass 28 ( 120 ) and mass 29 ( 130 ) ion traces.
  • the mass 30 ion trace 110 is chromatographically offset from the mass 28 and 29 ion traces 120 and 130 (i.e., mass 30 appears after the mass 28 and mass 29 ion traces).
  • the NO gas is comprised of [14]N[16]O, meaning that [14]N normally measured within the mass 28 and mass 29 ion traces, which are used in the calculations for % N and/or ⁇ 15 N, is not taken into account. From an isotopic perspective, if NO leaves the reactor because of an incomplete reduction to N 2 , then the measured ⁇ 15 N values will be inaccurate and imprecise.
  • the reactors described herein are adapted to enable a stoichiometric reduction of NO x gas species to N 2 before the analyte gas is conveyed from the reactor for separation and subsequent analysis by TCD and/or MS (such as IRMS).
  • the reactors can provide the following characteristics of elemental analysis:
  • reactors for combustion and/or reduction processes by continuous flow (more specifically, plug flow) elemental analysis interfaced with IRMS and/or quantitative elemental concentration analysis by standalone elemental analysis typically have a length in a range inclusive of between 20 mm and 470 mm, and an internal diameter in a range of between 0.1 mm and 46 mm, and they can be used in any gas elemental analysis system that employs chromatography and/or adsorption/thermodesorption techniques to separate gas mixtures.
  • elemental analysis systems described herein are suitable for other systems that rely on reactors for combustion and/or reduction processes, such as gas chromatography and gas chromatography interfaced with mass spectrometry (such as IRMS, but potentially other MS such as quadrupole MS, ion trap MS, time-of-flight MS, Fourier transform MS, and the like).
  • gas chromatography and gas chromatography interfaced with mass spectrometry such as IRMS, but potentially other MS such as quadrupole MS, ion trap MS, time-of-flight MS, Fourier transform MS, and the like.
  • an elemental analysis system 200 includes a reactor 210 having at least one reduction reaction zone 220 ( 3 reduction reaction zones 220 - 1 , 220 - 2 , and 220 - 3 shown in FIG. 2B ) including a metal zeolite that can reduce nitrogen oxides (NO x ) to molecular nitrogen (N 2 ) by selective catalytic reaction.
  • the reactor 210 is shown in a vertical orientation, the reactor 210 can be in a horizontal orientation, or oriented at any angle in-between vertical and horizontal.
  • a suitable metal zeolite has a copper content of 2.8 wt %, and a BET surface area of 358 m 2 /g. CuCZP 30E available from Clariant (Bruchmal, Germany).
  • the metal zeolite can have a grain size in a range of between 0.3 mm and 2.9 mm, such as in a range of between 1 mm and 2 mm, or, in a specific embodiment, the grain size of the metal zeolite can be 1.6 mm.
  • the metal zeolite includes carbon in an amount that is at least 70 ppm and less than 200 ppm, such as 100 ppm. The carbon content is believed to improve the thermal stability of the metal zeolite, enabling higher temperature operation of the reactor 210 .
  • the at least one reduction reaction zone 220 is one zone packed in a single packing unit having a length that is in a range of between 0.1% and 50% of a length of the reactor, such as in a range of between 1% and 30%.
  • the reduction reaction zone 220 has a length of 100 mm, packed in a reactor 210 having a length of 470 mm.
  • the reactor 210 includes an oxidation reaction zone 230 , the oxidation reaction zone 230 being located before the reduction reaction zone 220 in a direction of gas flow through the reactor 210 indicated by inlet and outlet arrows.
  • the reactor 210 optionally includes an oxygen gas inlet 235 upstream of or into the oxidation reaction zone 230 .
  • 2 ml/sample of O 2 were injected through the oxygen gas inlet 235 .
  • the reactor 210 includes a carrier gas inlet 225 upstream of the oxidation reaction zone 230 , for injecting carrier gas, such as helium, into the reactor 210 .
  • the oxidation reaction zone 230 includes an oxygen-donor material, such as at least one of chromium trioxide (Cr 2 O 3 ), tungsten trioxide (WO 3 ), copper oxide, and a mixture of copper oxide and platinum-coated aluminum oxide.
  • the length of the oxidation reaction zone 230 is in a range of between 1% and 30% of the length of the reactor 210 , preferable in a range of between 4% and 15% of the length of the reactor 210 .
  • the oxidation reaction zone 230 has a length of 50 mm.
  • the oxygen capture zones 240 - 1 and 240 - 2 comprise metallic copper, in two zones each having a length of 20 mm, or two zones of successively increasing length in a direction of gas flow through the reactor, e.g., 20 mm preceded by 10 mm separated by a porous material, such as quartz or glass wool.
  • the at least one reduction reaction zone can be two reduction reaction zones 220 - 1 and 220 - 2 of substantially the same length, the lengths being in total in a range of between 1% and 30% of the length of the reactor 210 , each reduction reaction zone having a length in a range of between 1% and 15% of the length of the reactor 210 .
  • the two reduction reaction zones 220 - 1 and 220 - 2 can have successively increasing lengths in a direction of gas flow through the reactor, the lengths being in total in a range of between 1% and 30% of the length of the reactor 210 .
  • the second reduction reaction zone 220 - 2 is at least 1.1 times longer, or at least 1.2 times longer, or at least 1.5 times longer, or at least 2 times longer, or at least 2.5 times longer, or at least 3 times longer, or at least 4 times longer than the first reduction reaction zone 220 - 1 .
  • the second reduction reaction zone 220 - 2 is up to 6 times longer, or up to 5 times longer, or up to 4 times longer than the first reduction reaction zone 220 - 1 .
  • the zones can be separated from each other by a porous material, such as quartz or glass wool.
  • the separation between reduction zones filled with porous material can have a length in a range of between 1% and 10%, preferably a length in a range of between 1% and 3%, of the length of the reactor.
  • the separation has a length of 0.5 cm or 1 cm, preferably 1 cm, for a reactor having a length of 470 mm.
  • the at least two reduction reaction zones can be three reduction reaction zones 220 - 1 , 220 - 2 , and 220 - 3 .
  • the relative lengths of the first and second reduction reaction zones can be as described above for the two zone reactor shown in FIG. 2D .
  • the third reduction reaction zone 220 - 3 is at least 1.1 times longer, or at least 1.2 times longer, or at least 1.5 times longer, or at least 2 times longer, or at least 2.5 times longer, or at least 3 times longer, or at least 4 times longer than the second reduction reaction zone 220 - 2 .
  • the third reduction reaction zone 220 - 3 is up to 3 times longer, or up to 2 times longer, or up to 1.5 times longer than the second reduction reaction zone 220 - 2 .
  • the first reduction reaction zone 220 - 1 has a length of 10 mm
  • the second reduction reaction zone 220 - 2 has a length of 40 mm
  • the third reduction reaction zone 220 - 3 has a length of 50 mm. More than three reduction reaction zone scan be provided in some embodiments.
  • the reactor zones graded in the way described herein provide a chemical gradient that increases the reaction speed and degree of reaction completion.
  • the elemental analysis system further includes a furnace 211 shown in FIG. 2A to heat the reactor 210 , wherein the reduction reaction zone 220 and oxidation reaction zone 230 are each configured to be heated to a temperature in the range of between 150° C. and 1,200° C., such as a temperature in the range of between 750° C. and 1,200° C., or a temperature in the range of between 950° C. and 1,100° C.
  • the elemental analysis system 300 can further include a second reactor 305 in fluid communication with a first reactor 310 , the second reactor 305 being located upstream in a direction of gas flow through the first reactor 310 , the second reactor 305 including an oxidation reaction zone 330 .
  • the first reactor 310 contains the at least one reduction reaction zone as described for FIGS. 2A-2D but without the oxidation reaction zone, which is instead located in the separate, second reactor 305 .
  • the elemental analysis system 300 can further include a furnace 315 surrounding the first reactor 310 to heat the first reactor 310 to a temperature in the range of between 450° C.
  • the second reactor 305 can further include an oxygen gas inlet 335 upstream of or into the oxidation reaction zone 330 for selectively permitting introduction of oxygen gas to the oxidation reaction zone 330 .
  • the second reactor 305 can further include a carrier gas inlet 337 for selectively permitting flow of carrier gas into the reactor 305 , for example, the inlet 337 can be located at the upstream end of the reactor 305 .
  • Sources of He gas and O 2 gas in the form of gas bottles 338 and 339 , respectively, are shown in FIG. 3A .
  • the oxidation reaction zone 330 can include an oxygen-donor material, such as at least one of chromium trioxide (Cr 2 O 3 ), tungsten trioxide (WO 3 ), copper oxide, and a mixture of copper oxide and platinum-coated aluminum oxide.
  • an oxygen-donor material such as at least one of chromium trioxide (Cr 2 O 3 ), tungsten trioxide (WO 3 ), copper oxide, and a mixture of copper oxide and platinum-coated aluminum oxide.
  • a Sulphur/halogen trap 350 is optionally located between 0 cm and 10 cm from the bottom of the second reactor 305 .
  • the Sulphur/halogen trap 350 can comprise i) silvered cobaltous oxide and/or silver vanadate, or ii) silver wool, packed in a length in a range of between 1% and 15% of the length of the second reactor 305 , either in a single zone or multiple zones.
  • the silver wool is preferably packed in a length in a range of between 1% and 8% of the length of the second reactor 305 .
  • the reactors 305 and 310 are fluidly connected via a stainless steel/sulfinert capillary 312 , which may or may not be separately heated above 100° C. to minimize water condensation.
  • the reduction reaction zones 320 are three reduction reaction zones 320 - 1 , 320 - 2 , and 320 - 3 .
  • the third reduction reaction zone 320 - 3 is at least 1.1 times longer, or at least 1.2 times longer, or at least 1.5 times longer, or at least 2 times longer, or at least 2.5 times longer, or at least 3 times longer, or at least 4 times longer than the second reduction reaction zone 320 - 2 .
  • the third reduction reaction zone 320 - 3 is up to 3 times longer, or up to 2 times longer, or up to 1.5 times longer than the second reduction reaction zone 320 - 2 .
  • the first reduction reaction zone 320 - 1 has a length of 10 mm
  • the second reduction reaction zone 220 - 2 has a length of 40 mm
  • the third reduction reaction zone 320 - 3 has a length of 50 mm, in a first reactor 310 having an overall length of 470 mm.
  • the reactor 310 also optionally includes at least one oxygen capture zone 340 (two oxygen capture zones 340 - 1 and 340 - 2 shown in FIG.
  • the total length of the oxygen capture zone 340 is in a range of between 1% and 15%, preferably in a range of between 1% and 8%, of the length of the reactor 310 .
  • the oxygen capture zones 340 - 1 and 340 - 2 comprise metallic copper, in two zones each having a length of 20 mm, or two zones of successively increasing length in a direction of gas flow through the reactor, e.g., 20 mm preceded by 10 mm separated by a porous material, such as quartz or glass wool.
  • the gases are carried out of the reactor 210 (or the first reactor 310 , not shown), they are swept through a water trap 260 (e.g., magnesium perchlorate) and/or a CO 2 /acid gas trap (e.g., carbosorb, not shown).
  • the reactor 210 is interfaced to a gas chromatography column 270 located downstream of the reactor 210 in a direction of gas flow.
  • the reactor can be interfaced directly with a mass spectrometer 280 located downstream of the reactor 210 in a direction of gas flow through the reactor 210 , optionally an isotope ratio mass spectrometer 280 of the magnetic sector multicollector type, as shown in FIG. 2A .
  • the gas chromatography column 270 can be interfaced to a thermal conductivity detector (TCD) 275 , or a flame ionization detector (FID) (not shown), an infrared (IR) detector (not shown), or a mass spectrometer, such as an isotope ratio mass spectrometer 280 , as shown in FIG. 2A .
  • the mass spectrometer is located downstream of the gas chromatography column 270 in a direction of gas flow, optionally an isotope ratio mass spectrometer including a magnetic sector mass analyzer.
  • the gas inlet of the mass spectrometer can comprise an open split as shown in FIG. 2A , wherein the analyte gas (e.g., CO 2 and/or N 2 etc.) is diluted with further carrier gas prior to introduction into the mass spectrometer, as known in the art.
  • the first reactor 310 is interfaced to a gas chromatography column 370 located downstream of the first reactor 310 in a direction of gas flow and downstream of an optional water trap 360 (e.g., magnesium perchlorate) and/or a CO 2 /acid gas trap (e.g., carbosorb, not shown).
  • the gas chromatography column 370 can be interfaced to a thermal conductivity detector (TCD) (not shown), or a flame ionization detector (FID) (not shown), an infrared (IR) detector (not shown), or a mass spectrometer, such as an isotope ratio mass spectrometer (not shown).
  • the first reactor can be interfaced directly with a mass spectrometer (not shown) located downstream of the first reactor 310 in a direction of gas flow through the first reactor 310 .
  • the mass spectrometer is, optionally, an isotope ratio mass spectrometer.
  • An open split gas inlet interface into the mass spectrometer is shown in FIG. 3A .
  • the elemental analysis system 200 includes an autosampler 255 , located upstream from the reactor 210 , for introducing liquid 255 - 1 or solid 255 - 2 samples into the system 200 .
  • the elemental analysis system 300 includes an autosampler 355 located upstream from the second reactor 305 for introducing liquid or solid samples into the system 300 .
  • the samples are commonly sealed in tin capsules (alternatively, silver or aluminum capsules) and introduced to the combustion reactor 305 by the autosampler 355 in a flow of carrier gas.
  • the capsule is broken down by heat and/or combustion in the reactor 305 , releasing the sample, which is then broken down to form combustion products containing its elemental components.
  • a method 400 of elemental analysis of a sample includes at step 410 introducing into an oxidation reaction zone a sample to be analyzed.
  • the sample can be sealed in tin capsules (alternatively, silver or aluminum capsules), and, optionally, introduced by, at step 405 , loading the samples into an autosampler prior to introduction to the reactor for processing.
  • the method then comprises oxidizing at step 420 the sample in the oxidation reaction zone to generate oxidized products including nitrogen oxides (NO x ) from nitrogen present in the sample, reducing at step 430 the nitrogen oxides to elemental nitrogen in a reactor including at least one reduction reaction zone including a metal zeolite that can reduce nitrogen oxides (NO x ) to molecular nitrogen (N 2 ) by selective catalytic reaction, and analyzing at step 440 the elemental nitrogen using mass spectrometry.
  • the analyzing can include analyzing the molecular nitrogen (N 2 ) using isotope ratio mass spectrometry (IRMS) and determining therefrom isotope abundances or an isotope ratio [14]N/[14]N, [15]N/[14]N, and/or [15]N/[15]N, or a ⁇ 15 N value for the nitrogen from the sample material.
  • IRMS isotope ratio mass spectrometry
  • the mass 30 peak can elute substantially simultaneously with mass 28 and mass 29 peaks in the IRMS analysis indicating it is due to N 2 rather than NO and therefore that the NO x to N 2 reduction reaction has been stoichiometric.
  • the method can optionally further include at step 450 introducing oxygen upstream of and into the oxidation reaction zone.
  • the behaviour of the mass 30 ion trace 510 has been completely altered.
  • the mass 30 ion trace 510 is linearly correlated to that of the mass 28 and mass 29 ion traces 520 and 530 , respectively, and chromatographically coherent. Consequently, the accuracy and precision of ⁇ 15 N values has significantly improved as determined on international isotopic reference materials.
  • FIG. 6 a linear correlation was observed between the intensity of the mass 30 and mass 28 ion traces from 166 contiguous samples processed within one reactor as shown in FIGS. 2A and 2B .
  • the reactor of the present invention can be used in a GC-MS, or GC-IRMS instrument (for example based on a Thermo Scientific Isotope Ratio Mass Spectrometer).
  • the reactor of the present invention can be employed in an LC-IRMS system, for example of the type described in US 2011-212536 A, the contents of which is incorporated herein in its entirety.
  • a chromatography column gas or liquid chromatography column
  • the elemental analysis and/or isotope ratio analysis can then be performed on the separated compounds in sequence, or on selected compounds eluting from the column.
  • the sample is typically injected into a gas chromatography (GC) inlet where it is carried into a chromatographic column by a carrier gas (e.g. helium).
  • a carrier gas e.g. helium
  • the sample and carrier gas flows through the column and the different compounds in the sample become separated and elute from the column at different times (retention times).
  • the separate compounds eluting from the chromatographic column in sequence then pass through the reactor (i.e. comprising the oxidation reactor to combust the compounds, followed by the reduction reactor to reduce nitrogen oxides to nitrogen).
  • a switching valve can be placed between the column and the reactor, which can be switched at the appropriate time, so that only compounds of interest can be selected and directed into the reactor, with compounds not of interest being directed to a waste line or similar at other times.
  • the same options for chemical traps as described hereinabove may be used in the system.
  • the oxidized/reduced gases are then introduced, optionally via a further gas chromatography column to separate the gases, into the ion source of the mass spectrometer, optionally via an open split interface, for elemental analysis and/or isotope ratio analysis.
  • FIG. 7 Such a system for GC is shown in FIG. 7 , which is analogous to the system of FIG.
  • the reactor is interfaced to a chromatography column, especially a gas chromatography column, located upstream of the reactor, preferably wherein an isotope ratio mass spectrometer is located downstream of the reactor.
  • a further chromatography column 270 especially a gas chromatography column, can be located downstream of the reactor, i.e. intermediate between the reactor and the mass spectrometer.
  • FIG. 9 shows a set of chromatograms obtained from sample analysis by GC-MS from an elemental analysis system according to a single reactor prior art embodiment, wherein the reduction reactor comprises metallic copper.
  • chromatogram (i) of FIG. 9 the total ion current (TIC) trace from the mass spectrometer measurement is shown and chromatogram (iv) shows the evolution of the N 2 species (masses 28 , 29 , 30 ).
  • the size of the mass resolved NO peak in chromatogram (iii) is significant in relation to the N 2 , i.e. the N 2 and NO are both present in relatively similar amounts, showing an incomplete NO x conversion, which affects the shape of the mass 30 15 N 2 chromatogram in chromatogram (ii).
  • FIG. 10 shows a set of chromatograms obtained from sample analysis by GC-MS from an elemental analysis system according to a single reactor exemplary embodiment of the invention.
  • the NO trace is virtually absent (below the limit of detection), because of the quantitative conversion of NO to N 2 on the zeolite in the reduction reactor. Accordingly, the shape of the N 2 traces (ii) and (iv) are improved and align well with the TIC trace (i).

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